Preparation of polyfluoroalkyl esters of fumaric and related acids

ABSTRACT

a process for the preparation of ester compounds of the formula: WHEREIN M IS AN INTEGER OF 3 TO 18; N IS AN INTEGER OF 2 TO 10; AND R is an ethylenically unsaturated hydrocarbon radical derived from fumaric, maleic, citraconic, mesaconic, or itaconic acid, which comprises reacting the compound CmF2m 1-CnH2nX wherein m and n are as defined above, and X is iodine, bromine or chlorine with a mono ammonium salt of fumaric, maleic, citraconic, mesaconic, or itaconic acid. In preferred embodiment, the monotriethylammonium fumarate is reacted with 1,1,2,2tetrahydroperfluoroalkyl iodide. Yields in excess of 50 percent are obtained. The esters prepared by the process of this invention form polymers which are useful in oil and waterrepellent textile finishes.

United States Patent Knellet al.

[54] PREPARATION OF POLYFLUOROALKYL ESTERS OF FUMARIC AND RELATED ACIDS [72] Inventors: Martin Knell, 4 Possum Rd., Ossining, NY. 10562; Edward Berger, 698 Yonkers ave, l

[22] Filed: June 2, 1969 [21] Appl. No.: 829,764

[52] ILLS. Cl. ..260/485 F, 117/1395 [51] Int. Cl. ,.C07c 69/52, C07c 69/60 [58] Field of Search ..260/485 F, 475

[56] References Cited UNITED STATES PATENTS 2,610,205 9/1952 Trigg et al. ..260/475 3,148,207 9/1964 Weinkauff et a1. ..260/485 Primary Examiner-Lorraine A. Weinberger Assistant Examiner-E. Jane Skelly Attorney-Karl J. Jorda and Bruce M. Collins 1 1 Aug. 22, 1972 5 7] ABSTRACT a process for the preparation of ester compounds of the formula:

0 II [on Fi -cum 0-c1t fluoroalkyl iodide. Yields in excess of 50 percent are obtained. The esters prepared by the process of this invention form polymers which are useful in oil and water-repellent textile finishes.

21 Claims, N0 Drawings PREPARATION OF POLYFLUOROALKYL ESTERS OF FUMARIC AND RELATED ACIDS This invention concerns a process for the preparation of ester compounds of the formula:

wherein m is an integer of 3 to 18, preferably 6 to 12 and most preferably 6 to n is an integer of 2 to 10 and is preferably 2 or 3, and most preferably 2; R is an ethylenically unsaturated hydrocarbon radical derived from fumaric, maleic, citraconic, mesaconic, or itaconic acid, preferably maleic or fumaric acid.

These compounds may be polymerized to polymers which are valuable in forming fabric finishes having excellent soil repellent properties. The oil and water repellent finishes of textiles treated with compositions containing such polymers are generally fast to repeated washing and dry-cleaning and thus retain their excellent soil repellency for long durations.

Particularly preferred polymers of a monomer which is prepared by the process of this invention are those of bis 1,1 ,2,Z-tetrahydroperfluorononyl) fumarate.

The compounds for which the process of the present invention may be employed are the subject of co-pending application Ser. No. 720,370 filed Apr. 10, 1968 assigned to the assignee of the present application.

Up to the time of the present invention, methods used for the preparation of such compounds were often uneconomical and in some instances, required extremely long reaction times.

Generally, known processes for preparing the corresponding methacrylate esters from a perfluoroalkyl iodide and an alkali metal salt of the acids cannot be adapted to the preparation of the esters of Formula I because little or no product is obtained and/or special solvent systems are required.

The present invention comprises polyfluoroalkyl halide of the formula:

m 2m 2. X wherein m and n are as defined in Formula I and X is reacting a trans) iodine, bromine, or chlorine, preferably iodine, with a mono ammonium salt of fumaric, maleic, citraconic,

mesaconic, or itaconic acid wherein the amine is selected from the group consisting of di and trialkylamines wherein the alkyls are one to four carbon atoms in length, morpholine, N-loweralkylmorpholine, piperidine, triethyleneldiamine, aniline or dimethylaniline, and most preferred, a triethylamine; at a temperature from above the melting point of the reactants to approximately 200C, from one-half hour to 30 hours. Where the term lower alkyl is used, there is intended alkyl of one to four carbon atoms.

Thepolyfluoroalkyl halide used in the above formula may be prepared by procedures well known to those skilled in the art. For example, the preparation of polyfluoroalkyliodides of the above formula are disclosed in US. Pat. No. 3,145,222 Brace.

It is to be understood that the perfluoroalkyl group may be, and usually is, a mixture of different chain lengths since the basic starting materials are obtained by telomerization procedures which yield perfluoroalkyl halides of varying lengths. The starting compounds comprising a single chain length may readily be obtained if desired by separation or synthetic techniques well known to the art.

The salts of the acids employed may be prepared by mixing the acid with a stoichiometrically equivalent amount of the appropriate amine in water, acetone or methanol, heating to dissolve if necessary, and evaporating to dryness to recover the salt.

It is particularly surprising that completely unsatisfactory yields or extensive reaction times were required if the preparation of the desired esters was attempted from di salts of the acids, whereas employing the above mono amino salts, much higher yields were obtained and shorter reaction times could be employed. Also the necessity of any solvent was eliminated.

It is especially surprising that in most instances the di salt of the above amines and acids cannot be formed by the usual methods but only the mono salt is obtained even if excess amine is used. The overall scheme involving the process of the present invention can be exemplified by following the series of reactions employed in the preparation of the his (l,l,2,2-tetrahydroperfluorononyl) fumarate from l,l,2,2-tetrahydroperfluorononyl iodide and the monotriethylammonium salt of fumaric acid.

0 0 OH 0 0 011 E (021mm trans coon ooonfuogmn As mentioned above, the temperature can range from just above the melting point of the reactants to approximately 200C. At lower temperatures, the reaction proceeds much more slowly and at the higher temperatures, some decomposition takes place. A generally suitable range of temperature is 100l75C and a preferred range is 125l75C. It has generally been found that the most desirable range is l40-l60 C.

The times of reaction may be varied between onehalf hour to 30 hours. If a stoichiometric amount of the ammonium salt is employed, reaction times of approximately 20 to 25 hours are usually required. Surprisingly, however, it has been observed that if two to three times the required amount of the mono ammonium salt is employed, the reaction times are usually reduced to the order of 5 hours.

Also as indicated above, a primary advantage of the present invention is the elimination of the need for any solvent system. In some cases, we have found that slightly improved yields may be obtained by employing the desired product as a solvent, whereas other solvents do not appear to have any significant influence on yields when employing the process of the present invention.

The following examples describing certain representative embodiments of this invention will serve to further illustrate the nature of this invention. The examples are illustrative and intended to enable those skilled in the art to practice the invention in all of the embodiments flowing therefrom.

EXAMPLE 1 Bis l ,1 ,2,2-Tetrahydroperfluoroalkyl) Fumarate a. Monotriethylammonium Fumarate Three hundred forty-eight g (3.0 moles) of fumaric acid is slurried in 1050 ml of acetone, cooled to C and 303 g (3.0 moles) of triethylamine added slowly with stirring and cooling so as to keep the temperature below 30C. After the addition, stirring is continued for 1 hour, and the reaction mixture then filtered. After drying in a vacuum oven at 60C, the monotriethylammonium fumarate weighs 640.0 g (98 percent yield) and melts at 90-93C.

b. Bis 1,1,2,2-Tetrahydroperfluoroalkyl) Fumarate Eight hundred g (1.40 moles) of perfluoroalkyl iodide was mixed with 620 g (2.85 moles) of triethylammonium fumarate in a 2 liter flask equipped with stirrer, thermometer and condenser leading to a dry-ice trap. The apparatus is purged with nitrogen and then the reaction mixture heated with vigorous stirring at 135-l 50C for 9 /2 hours, after which a VPC of the lower layer shows no significant R,CH CH l remaining. While still at 150C, the volatile olefins are distilled into the dry-ice cooled trap, first at atmospheric pressure and then at reduced pressure down to 2 mm. While still hot, the reaction mixture is poured into a separatory funnel and the bottom layer drawn off. The lower layer, which weighs 421.2 g is distilled in a molecular still at 150Cl60C and 1 micron pressure. The cold finger condensing surface is kept at 80C with a circulating constant temperature bath so as to keep the distillate liquid. The distillate, which consists of a mixture of fumarate diesters having R, chain lengths of C C weighs 340 g. On hydrolysis with 0.2 N aqueous potassium hydroxide, the resulting alcohol mixture has the following composition (extraction into chloroform and VPC analysis):

avc. M.W. of R,CH CH,OH =452 avc. M.W. of fumarate diesters 984 The conversion of R,CH CH l to diester for the different chain lengths is approximately as follows:

Converted to R, Dicster, C F 43.5 C,,F,,- 57.0 C F 53.5 C F 24.5

The overall conversion to the desired fumarate diester was 49.5 percent.

The perfluoroalkyl iodide employed boiled at C/ 1 00 mm to 132C/ 1 5 mm and was comprised of:

Weight C F CH CH- l 35.3 C F CH CH I 33.4 c,,F,,cH,cH,i 24.2 C F CH CH I 4.45 C F CH CHJ 0.74 2 impurities 1.86

ave. M.W. of RICHZCH2I= 561.

EXAMPLE 2 Bis l ,1,2,Z-Tetrahydroperfluoroalkyl) Fumarate a. Monotriethylammonium Six thousand gms (51.7 moles) of fumaric acid and 46,000 mls of anhydrous acetone are charged into a 20 gallon resin flask equipped with a stirrer, thermometer, pressure-equalized dropping funnel and cooling bath. The stirred suspension is cooled to 15C and 5,225 gms (51.7 moles) of triethylarnine added over a period of one-half to 1 hour while the temperature is maintained at 1520C. An additional 4,000 mls of acetone are added to facilitate stirring, and stirring continued for an additional hour at room temperature. The suspension is filtered by suction and the fumarate salt washed three times with 4,000 mls of acetone and dried to constant weight at 40C in vacuo. The product obtained is a white crystalline solid, m. p. 9l-94C with a 97-percent yield. Perchloric acid titration of a sample of the fumarate salt gives a neutral equivalent of 218.8, calculated 217.

b. Bis l ,l ,2,Z-Tetrahydroperfluoroalkyl) Fumarate Eight thousand nine hundred forty-two gms (15.1 moles) of 1,l,2,2-tetrahydroperfluoroalkyl iodide and 6,500 gms (30 mols) of triethylammonium fumarate are charged into a 22 liter, 3-neck round bottom flask fitted with a bottom stopcock and equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and heating mantles. The reaction mixture is heated with stirring to C over 1 hour under a very slow stream of nitrogen and stirred at flfor 2324 hours. After 21-22 hours, a sample of the lower layer by VPC indicates less than 2 percent of the starting iodide remaining. After 23-24 hours, stirring is stopped and the two dark molten phases allowed to separate into layers over a period of 1015 minutes.

95-100bLC over a period of 2-3 hours. The crude fumarate diesters are obtained, at room temperature, as a brown, waxy solid weighing 5 ,094 gms.

Half of the crude product, 2,540 gms, is distilled at high vacuum through a short (8 inch) insulated column without a condenser. The main fraction, boiling at 138-2l4/0.02-0.03 mm and weighing 1,868 gms, is obtained on cooling as a yellow solid.

The once distilled fumarate diester mixture is further purified as follows: The product weighing 1,868 grns is melted and poured at 100-110C into 2,000 mls of dimethylformarnide at room temperature with rapid hand stirring. The mixture is cooled in ice water to C, then filtered by suction and sucked as dry as possible. The wet filter cake without washing is remelted in a 4 liter resin flask and poured into 2,000 mls of benzene with hand stirring, cooled to 15C as before, and the crystallized solid refiltered. The product is washed twice with 1,000 mls of benzene and dried in vacuo at room temperature to constant weight. The purified diester mixture is obtained as an almost colorless, waxy, granular solid weighing 1,442 gms. The purified product, 1,432 gms, is finally redistilled and the fraction boiling at 144176/0.02 mm collected as bis (l,1,2,2-tetrahydroperfluoroalkyl) fumarate, a white waxy solid at room temperature, weight 1,369 gms.

The other half of the crude product, 2,540 gms, is distilled, boiling point 150l85/0.03 mm, yielding 1,970 gms; washed and dried as described above but with benzene only, giving 1,725 gms; and finally redistilled to yield 1,540 gms of his (1,1,2,2- tetrahydroperfluoroalkyl) fumarate, boiling point 150182/0.02 mm. The total weight of the fumarate diesters is 2,909 gms.

A repeat preparation carried out with 14.9 moles (8,814 gms) of 1,l,2,Z-tetrahydroperfluoroalkyl iodide gave 2,821 gms of product.

The preparation of the monotriethylammonium fumarate is repeated by reacting 1 equivalent of fumaric acid and 2 equivalents of triethylamine in methanol. A sample of the product is titrated with perchloric acid and gives a neutral equivalent of 221. The calculated equivalent of the mono salt is 217, that of the di salt 159.

Analysis for C H N O Calc.: C, 55.2 H, 8.84; N, 6.45 Found: C, 55.01; H, 8.86; N, 6.55

EXAMPLE 3 Bis 1,1,2,2-Tetrahydroperfiuoroalkyl) Fumarate a. Monotriethylammonium fumarate Six thousand gms (51.7 moles) of fumaric acid and 40,000 mls of acetone are mixed in a stirred suspension, cooled to 15C and 5,225 gms (51.7 moles) of triethylamine added over a period of one hour while the temperature is maintained at 1520C. An additional 10,000 mls of acetone were added to facilitate stirring since the suspension becomes quite thick toward the end of the addition of triethylamine. Stirring is continued for 1 hour after the addition is complete, and the suspension filtered by suction. The filter cake is washed three times with 4,000 mls of acetone and dried to constant weight at 40C in vacuo. The product obtained is a white crystalline solid weighing 1 1,003 gms, 98 percent of theory, m.p. 91-94C.

b. Bis 1,1,2,2-Tetrahydroperfluoroalkyl) Fumarate Ten thousand gms (17 moles) of l,1,2,2- tetrahydroperfluoroalkyl iodide are heated to 90C and together with 7,260 gms (33.4 moles) of triethylammonium fumarate are heated together with efficient stirring to C over 1% hours under a very slow stream of nitrogen and stirred at i5 for 23-24 hours. After 21-22 hours, a sample of the lower layer by VPC indicates less that 1% of the starting iodide remaining. After 2324 hours, stirring is stopped and the two dark molten phases allowed to separate into layers over a period of 1015 minutes. The clear, dark brown lower layer amounting to 7,888 gms is drawn off slowly. The volatile olefins are stripped off at 5 mm and a bath temperature of 90100C over a period of 2-3 hours. The residue, consisting of crude fumarate diesters is obtained as a brown, waxy solid weighing 5,462 gms.

Half of the crude product, 2,778 gms, is distilled at high vacuum through a short (8 inch) insulated column without a condenser. After the collection of 257 g of forerun, b. p. 30147/0.02 mm, the main fraction, boiling at 152203/0.02 mm and weighing 2,082 gms is obtained on cooling as a yellow solid containing dark colored impurities which codistilled. The second half of the crude product, 2,675 gms, is distilled in the same way to yield 2,075 gms ofa main fraction, b. p. 155-l9 5/0.03 mm.

The once distilled fumarate diester is further purified as follows: The two main fractions are melted, combined (total 4,157 gms), and poured at 100-110C into 4,000 mls of dimethylformamide at room tempera ture with rapid hand stirring. The mixture is cooled in ice water to 15C, then filtered by suction. The wet filter cake, without washing, is remelted in a 5 liter resin flask and poured into 4,000 mls of benzene with hand stirring, cooled to 15C as before, and the crystallized solid refiltered. The filter cake is triturated with 3,000 mls of benzene at room temperature, again filtered, washed with 2,000 mls of benzene and dried in vacuo at room temperature to constant weight. The purified diester mixture is obtained as an almost colorless, waxy, granular solid weighing 3,023 gms. The purified product, 3,013 gms, is finally redistilled in two portions to yield 1,429 gms, b. p. 1S0-185 /0.02 mm and 1,412 gms, b. p. 153- /0.01l mm, total, 2,841 gms (32 percent of theo y), of his (1,l,2,2-tetrahydroperfluoroalkyl) fumarate obtained as a white waxy solid at room temperature.

EXAMPLE 4 Bis l ,1,2,2,3,3-l-lexahydroperfiuorodecyl) Fumarate a. 1,1 ,2,3,3-Pentahydro-2-lodoper1luorodecyl Acetate sisobutyronitrile catalyst are added. The reaction mixture is then cooled to room temperature and distilled through a small spinning band column under reduced pressure. The portion boiling at 6872C/.05-.002 mm contains approximately 90 percent of pure product.

b. 1,1 ,2,3,3-Pentahydroperfluorodecene Nineteen g of zinc dust and 20 ml of anhydrous ethanol are added to a 500 ml flask and stirred rapidly while ml of 36 percent hydrochloric acid are added. The reaction mixture is heated to 60C and 50.0 g of 1,1,2,3,3-pentahydro-2-iodoperfiuorodecyl acetate added with 100 ml of anhydrous ethanol. The addition of the acetate takes approximately 45 minutes. The reaction mixture is continuously stirred for an additional 2 /2 hours and the temperature maintained at 60C. Thereafter the reaction mixture I is cooled to room temperature, the unreacted zinc is filtered off and the product extracted with 1,500 ml of water. The extracted layer is dried over molecular sieve and then distilled through an 18 inch spinning band column. 19.6 g of product boiling at 142144C/760 mm is obtained.

Analysis for c, H,F,, Calc.: C, 29.35; H, 1.12; F, 69.49 Found: C, 29.35; H, 1.32; F, 70.17

c. 1,1,2,2,3,3-Hexahydroperfluoro-l-Bromodecane 15.6 g of 1,1,2,3,3-pentahydroperfluorodecene are added to a quartz glass Fischer Porter tube and brought to boiling to remove any possible trapped air. It is then cooled to the temperature of liquid nitrogen and 7.0 g of dry hydrogen bromide added and the tube closed. The reaction mixture is allowed to warm to room temperature and it is then placed centimeters from a 250 watt UV light source for 4 /2 hours. The excess hydrogen bromide is permitted to escape the product is then washed with 50 ml of water to remove any trapped hydrogen bromide. It is then washed with 25 ml of a 10 percent solution of sodium thiosulfate and dried over molecular sieve, for four hours. Distillation yields a product boiling mainly at 9596C/24 Analysis for C H BrF Calc.: C, 24.46; 1.23; Br, 16.27; Found: C, 24.31; H, 1.27; Br, 17.50;

F, 58.04 F,58.l0

Analysis for C H F O Cale; C, 30.78; H, 1.51; F, 60.87 Found: C, 31.08; H, 1.62; F. 60.83

EXAMPLE 5 Bis 1 ,1 ,2,Z-Tetrahydroperfluorononyl) Fumarate a. 1 1 ,2,2-Tetrahydrol -Bromoperfluorononane 52.4 g of 1,1,2,2-tetrahydro-l-iodoperfluorononane, 17.6 g of bromine, and 0.5 g of benzoyl peroxide are charged into a Fischer Porter tube equipped with a magnetic up and down stirrer. The reaction mixture is heated with constant stirring to 95C for 1 /2 hours. An additional 9.6 g of bromine and 0.2 g of benzoyl peroxide are added and the reaction continued for an additional 4 hours. The product is washed with a solution containing 49.6 g of sodium thiosulfate and 500 ml of water. The lower layer is isolated and distilled in an 18 inch spinning band column. The product collected has a boiling point of 7880C/25 mm.

Analysis for C H BrF, Ca1c.: C, 22.71; H, 0.84; F, 59.74; Found: C, 22.41; H, 0.81; F, 60.64;

Br, 16.75 Br, 17.39

Fraction Boiling Point Pressure Weight 1 2565C mm 1.2 2 65103C 100 mm 1.8. 3 153-l94C 100mm 10.2

VPC shows cut no. 1 comprised 68% product; out no. 2 comprised 78.9 percent product; and cut no. 3 comprised 92.9 percent product. Yield: 52 percent.

EXAMPLE 6 Bis l ,1 ,2,Z-Tetrahydroperfluorononyl ltaconate a. Monotriethylammonium ltaconate 13.0 g (0.1 moles) of itaconic acid is dissolved in methanol and thereafter neutralized with 10.1 g (0.1 mole) of triethylamine and the solution evaporated to dryness. The liquid residue is dried in a vacuum desiccator for about 20 hours. It is titrated with 0.0991 normal perchloric acid to give an equivalent weight of 260.5 (theoretical 231) b. Bis l ,1,2,2-Tetrahydroperfluorononyl ltaconate 21.0 g (.04 mole) of 1,1,2,2-tetrahydroperfluorononyl iodide and 18.5 g (.08 mole) of monotriethylammonium itaconate from (a) are stirred together for 1% hours at C. VPC indicates 21.6 percent of the diester is formed. After 1 1% hours of heating at 140C, VPC indicates 48.5 percent conversion to the diester. The volatiles are removed at 140C/5 mm. The bottom layer is separated and weighs 6.6 g. The top layer is extracted with water and chloroform and washed with water three times. Thereafter the chloroform is distilled off leaving 5.3 g of residue which by VPC comprises 72 percent diester. This was mixed with 6.6 g of the bottom layer and distilled at .030 mm over 95C to C, yielding by VPC a total of 33.6 percent of the diester.

, formed as indicated by VPC, and the isolated yield are also indicated in the following TABLE 1.

4. A process as claimed in claim 1 wherein said temperature is in the range of 125C to 175C.

5. A process as claimed in claim 1 wherein said temperature is in the range of 140C to 160C.

6. A process as claimed in claim 1 wherein said amine is triethylamine.

7. A process as claimed in claim 1 wherein said acid is fumaric.

TABLE 1 Diostcr Fumurutu suit Reaction Reaction formed lexumph: Mole temperntime, percent Isolated number CiFiiCllzCllai Type Molt-s Solvent turc, 0. hrs by VPC yield 01 .\1ono(C11ii);N 08 Product 150 8 07 38 05 1\10no(C=lli);N.... .10 'lriiluoruiolucno. 160 7% 38 25 .02 Ml10(C:iis):N .02. N01\t....... 170 30 60 30 .00 l\iouo(C=lli);N...... .08 160 20 60 51 .04 l\louo(Czlli)iN.... 1150 my, 72 5'2. 6 .05 li10n0(CalIt)aN.-.... 130 0% 47 28.2 06 Mono plpcridlnm. 150-155 30 71 53. 8 .00 1\lO1'10(C:Hl)JN- 150 6 64 49. 8 00 Mono(Czlh):N. 150 6% 05 4B. 5 00 Mono(C:lii)iN. 100 (12 44. 0 .00 M0110(C:11;);N...... 125 10 60 54.5

EXAMPLES 18 27 in Examples 18 27, also following the general method set forth in previous examples, the following iodides and salts indicated in TABLE 11 are reacted employing the solvents, times and temperatures indicated in TABLE 11. in each instance, very satisfactory yields of the desired ester are obtained.

8. A process as claimed in claim I wherein said halide is a polyfluoroalkyliodide.

9. A process as claimed in claim 1 wherein n is 2, said acid is fumaric, and said temperature is in the range of 100C to 175C.

10. A process as claimed in claim 9 wherein said amine is a trialkylamine.

TABLE 11 Exnmple number iodide Acid salt Solvent Temperature Tlmu (CFilzCFClhClizl lilono-N-methyl morphoilnc oimalelc acid Product 200 30min. (Cl-i)(C1-":)i(Cl1=)4l Mono-tributyl unuuouium citrncouato...-. ..(io 125 4 hrs. (Cl-;) CF(CFz)|(Cll:)wl Mono-dhnetliyl ammonium mesnoouate. 'irliluorotolueue- 1' bhrs.

(I1-;(CF)iCll=Cli=Cli:l Mono-plpcridlllo salt 01 itaconic ncld Product... 175 ZOhrs. CFflCFghCllzClhl Mono'anlllno salt oiiumurlenciti l-octanol 150 30hrs. tlF tCFmcllzCiiil Mono-tr1propylnmmonlurnsnlt o1 imnnrlc acl Diglymc 140 25hrs. .2-1 CFflCFzleCilzCiizi Mono-trluthylnmmonlum snltoimesooonlc ncld Product. 180 10 hrs. ":5 (CFJhCi-(CFmCIlzCllri Mono- 11ethylnmmonlumsnlt oiiumurlc 0e10,. t-Amylnleohol. 100 bhrs. 26.. CFACFzhClhClizi Mono-trlcthylnmmoulumiumurate Dlmethyliormamlde- 160 Shrs. l7 UFflcFz)iuClizCiIzClhi Mono-trlethylummonlum iumnrute Ethylene glycol 100 6111's.

WECLAIM: 11. A process as claimed in claim 9 wherein said 1. A process for the preparation of an ester compound of the formula:

wherein m is an integer of3 to 18;

n is an integer of 2 to 10;

R is an ethyienically unsaturated hydrocarbon radical derived from fumaric, maleic, citraconic, mesaconic, or itaconic acid, which comprises reacting a polyfiuoroalkyl halide of the formula c F -C ,H wherein m and n are as defined above, and X is iodine, bromine, or chlorine with a mono ammonium salt of fumaric, maleic, citraconic, mesaconic, or itaconic acid formed from the acid and an amine, wherein the amine is selected from the group consisting of di and triloweralkylamines wherein the alkyls are 1-4 carbon atoms in length, morpholine, N-lowernlkylmorpholine, piperidine, triethylenediamine, aniline, or dimethyianiiine, at a temperature from above the melting point of the reactants to 200C.

2. A process as claimed in claim 1 wherein the reaction time is from one-half hour to 30 hours.

3. A process as claimed in claim 1 wherein said temperature is in the range of 100C to 175C.

amine is a triethylamine.

12. A process as claimed in claim 1 wherein an excess of the equivalent amount of the salt is employed.

13. A process as claimed in claim 4 wherein two to three times the equivalent amount of the salt is employed.

14. A process as claimed in claim 11 wherein two to three times the equivalent amount of the salt is employed.

15. A process as claimed in claim 11 wherein said temperature is in the range of C to C.

16. A process as claimed in claim 11 wherein said halide is a polyfiuoroalkyliodide.

17. A process as claimed in claim 16 wherein m is 6 to l2.

18. A process as claimed in claim 4 wherein m is 6 to 12, n is 2, X is iodine, said acid is fumaric, and said amine is a trialkyiamine.

19. A process as claimed in claim 18 wherein said temperature is in the range of 140C to 160C and said amine is triethylamine.

20. A process as claimed in claim 16 wherein two to three times the equivalent amount of the salt is employed.

21. A process as claimed in claim 18 wherein an excess of the equivalent amount of the salt is employed. 

2. A process as claimed in claim 1 wherein the reaction time is from one-half hour to 30 hours.
 3. A process as claimed in claim 1 wherein said temperature is in the range of 100*C to 175*C.
 4. A process as claimed in claim 1 wherein said temperature is in the range of 125*C to 175*C.
 5. A process as claimed in claim 1 wherein said temperature is in the range of 140*C to 160*C.
 6. A process as claimed in claim 1 wherein said amine is triethylamine.
 7. A process as claimed in claim 1 wherein said acid is fumaric.
 8. A process as claimed in claim 1 wherein said halide is a polyfluoroalkyliodide.
 9. A process as claimed in claim 1 wherein n is 2, said acid is fumaric, and said temperature is in the range of 100*C to 175*C.
 10. A process as claimed in claim 9 wherein said amine is a trialkylamine.
 11. A process as claimed in claim 9 wherein said amine is a triethylamine.
 12. A process as claimed in claim 1 wherein an excess of the equivalent amount of the salt is employed.
 13. A process as claimed in claim 4 wherein two to three times the equivalent amount of the salt is employed.
 14. A process as claimed in claim 11 wherein two to three times the equivalent amount of the salt is employed.
 15. A process as claimed in claim 11 wherein said temperature is in the range of 140*C to 160*C.
 16. A process as claimed in claim 11 wherein said halide is a polyfluoroalkyliodide.
 17. A process as claimed in claim 16 wherein m is 6 to
 12. 18. A process as claimed in claim 4 wherein m is 6 to 12, n is 2, X is iodine, said acid is fumaric, and said amine is a trialkylamine.
 19. A process as claimed in claim 18 wherein said temperature is in the range of 140*C to 160*C and said amine is triethylamine.
 20. A process as claimed in claim 16 wherein two to three times the equivalent amount of the salt is employed.
 21. A process as claimed in claim 18 wherein an excess of the equivalent amount of the salt is employed. 